shale exploration

Unconventional Methods For Unconventional Plays:

Using Elemental Data To Understand Shale Resource Plays
Ken Ratcliffe and Milly Wright, Chemostrat; Dave Spain, BP USA

Part 1

hales are an important hydrocarbon

resource; yet understanding them as
reservoirs remains problematic. Their
fine-grained, organic-rich yet superficially
homogenous character make the application
of traditional reservoir characterisation
methods impractical or impossible.
Increasingly, in the North American shale
plays, inorganic geochemical data are being
used as a one-stop method for understanding
shale reservoirs. For decades, elemental data
have been used to help solve stratigraphic
problems, i.e. definition of chemostratigraphic
frameworks. However, the same dataset
acquired for chemostratigraphic studies can
be used to model shale mineralogy, model
TOC levels, determine paleoredox conditions,
identify zones of biogenic silica in shales and
provide information about transgressive
regressive cycles.
The applications of elemental data to
understanding shale plays fall into two natural
groupings. The first is the traditional use of
geochemical data to aid in understanding
regional and reservoir-scale stratigraphy. This
application is discussed in this issue of PESA News
Resources. The second main use geochemical
data is in modeling applications, such as those
listed above, and this will be discussed in the
next issue of PESA News Resources.

equivalent resources of Canada, Mexico and

the United States and it exceeds the estimated
recoverable reserves of CSG in Australia.
Despite the activity and the large number of
well completions, the fine grained, macro-scale
homogeneity of many formations currently
being exploited in North America negates some
of the more traditional approaches to reservoir
characterisation and stratigraphic correlation,
which has resulted in the search for new
methodologies that enable better stratigraphic
understanding of shale reservoirs. Here, the
application and potential of one approach
is demonstrated, namely the application of
inorganic whole rock geochemical data (or
chemostratigraphy) to shale resource plays.
Inorganic whole rock geochemical data have
been used to define stratigraphic correlations
in the petroleum industry for over a decade
now (Ratcliffe et al., 2010 and references cited
therein). The technique of chemostratigraphy
relies upon recognising changes in element
concentrations through time and using those
to model changes in geological features, such
as paleoclimate (Pearce et al., 2005, Ratcliffe et
al., 2010) and provenance (Ratcliffe et al., 2007,

Wright et al., 2010). Published accounts using

this approach are largely on fluvial successions,
where stratigraphic correlation using traditional
techniques are often problematic (e.g. Pearce
et al., 2005, Ratcliffe et al., 2006, Ratcliffe et
al., 2010, Wright et al., 2010 and Hildred et al.,
2011). Over the same decade, inorganic whole
rock geochemical datasets have routinely been
acquired from mudrocks, the data typically
being used to help elucidate paleoredox
conditions during oceanic anoxic events (e.g.
Tribovillard et al., 2006, Turgen and Brumsack,
2006, Tribovillard et al., 2008, Negri et al.,
2009, Jenkyns, 2010). Here, approaches of the
chemostratigrapher and the oceanic anoxic
event are combined and pragmatically applied
to shale gas plays in North America.
While the applications presented here are largely
tested on the Haynesville Formation and, to a lesser
extent, the Eagle Ford and Muskwa formations,
the approaches adopted herein would be equally
applicable to any shale resource play.

Methodology and dataset

The data for this article are largely from the
Haynesville Formation, with less extensive datasets

Introduction
In the past decade, shale resource plays have risen
to the forefront of hydrocarbon exploration, as
shown by the numerous 'shale conferences' in the
past two years alone (Critical Assessment of Shale
Resource Plays, Hedberg Research Conference Dec
2010, Austin, Texas, World Shale Gas Conference
& Exhibition, Nov 2010, Dallas Forth Worth, Texas,
Nov 2011, Houston, Texas, Global Unconventional
Gas Conference, June 2010, Amsterdam, Shale
Gas World Europe, Dec 2010, Warsaw, Poland,
Shale Gas Insight 2011, Nov 2011 Philadelphia,
Pennsylvanian, Shale Gas Asia 2011, Feb, New
Delhi, India to name but a few). Although the
majority of active producing shale plays are in
North America, the success there has led to
increased interest in shale formations around the
world, including in Australia, where according
to a June 2011 report commissioned by the US
Energy Information Agency, Australia has 396 Tcf
of technically recoverable shale gas resources.
This is equivalent to about 20% of the combined

Fig. 1. Geographic location and ages of the shale reservoir plays referred to in the text.

February/March 2012 | PESA News Resources |

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shale exploration
from the Muskwa Formation and
the Eagle Ford Formation also
being drawn upon (Figure 1). All
of these formations are proven
shale gas plays, with each being
extensively drilled for exploration,
appraisal and production.
The Haynesville Formation is
late Jurassic (Kimmeridgian) in
age. It is a locally calcareous and
organic rich (TOC values are
2-6%) mudrock that occurs in
northeast Texas and northwest
Louisiana (Figure 1). It was
deposited in an extensive intra
shelf basin on the young,
passive margin of the US Gulf
Coast during a period of arid
climatic conditions. Basement
Fig. 2. Geochemical characterisation of the Haynesville Formation as penetrated in Well Watson-4. Logs for a series of key
faulting and salt movement
elemental ratios are plotted relative to depth in order to characterise broad scale Chemostratigraphic Packages (Plot
A) and finer scale geochemical units Plot B). All samples analysed here are from conventional core and all data were
controlled the initial water depths,
acquired using ICP OES MS with a Li-metaborate fusion preparation.
resulting in regions of the sea bottom
having restricted communication
Package 3 (transitional between the
palynomorphs are often thermally degraded.
with the open ocean and therefore

Haynesville and Bossier formations) is
Also, electric log correlations are hampered by
recurrently experiencing anoxic bottom water

identified by generally lower Fe2O3/MgO
the variable controls on U, K and Th. In typical
conditions. The Eagle Ford Formation is a dark

and Rb/K2O values compared to Package
fluvial and shallow oxic marine settings the K, Th,
grey calcareous, locally organic-rich mudstone

2 and lower Th/U values compared to
and U are all largely controlled by the amount
of Cenomanian Turonian age (Figure 1). It

Package 4.This interval also displays
of clay versus sand, enabling lithostratigraphic
sub-crops in south Texas forming a narrow strip

elevated CaO/Al2O3 values relative to
and sequence stratigraphic correlations to be
that is 150 miles long. Over this distance, the

Packages 2 and 4.
made from the gamma logs. However, in the
Eagle Ford Shale Formation varies in thickness
Haynesville Formation, U is associated with
from approximately 75 ft to 300 ft. The Muskwa
Package 2 (equivalent to the Haynesville
TOC and minerals derived from authigenic
Formation is Frasnian (Devonian) in age and is

Formation) is characterised by higher
enrichment in anoxic conditions, whereas
located in northern Alberta, northeastern British
Fe2O3/MgO values than underlying
K and Th are associated with the amount of
Colombia and in the southern portion of the

packages and lower Th/U and MgO/
terrigenous-derived material. These associations
Northwest Territories, Canada (Figure 1).

(CaO+MgO) values than the overlying
are discussed in greater detail in Part 2 of

Package 4.
this article. Therefore, using gamma logs for
All data for this article have been acquired using
stratigraphic correlations in shale gas plays is
Inductively Coupled Plasma Optical Emission
Package 1 (transitional between the
enigmatic. Furthermore, the apparent macro(ICP-OES) and Mass Spectrometry (ICP-MS),

Haynesville and Smackover formations)
scale homogeneity of the mud-rocks precludes
following a Li-metaborate fusion procedure

is characterised by CaO/Al2O3 values that
the recognition of sedimentary facies that can
(Jarvis and Jarvis, 1995). These preparation and

are intermediate between those of
be used for stratigraphic correlations, particularly
analytical methods provide data for 10 major

Packages 0 and 2, and lower Fe2O3/MgO
when only cuttings samples are available.
elements (SiO2, TiO2, Al2O3, Fe2O3, MgO, MnO,
CaO, Na2O, K2O, P2O5), 25 trace elements (Ba, Be,

values than overlying packages.
Co, Cr, Cs, Cu, Ga, Hf, Mo, Nb, Ni, Pb, Rb, Sc, Sn,
Chemostratigraphy has been used to
Sr, Ta, Tl, Th, U, V, W, Y, Zn, and Zr) and 14 rare
Package 0 (equivalent to the Smackover
characterise and correlate the Haynesville
earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb,

Formation) is identified by high CaO/Al2O3
Formation, along with underlying and
ratios.
Ho, Dy, Er, Tm, Yb, and Lu).
overlying portions of the Smackover and
Bossier formations respectively. Figure 2
It is possible to further subdivide the
shows a chemostratigraphic package and
Stratigraphic applications of
Haynesville Formation (Chemostratigraphic
unit level characterisation of the Haynesville
whole rock inorganic geochemical
Package 2) into a series of higher resolution
Formation in a single well. On Figure 2a the
data in shales
Chemostratigraphic Units; 2.1, 2.2, 2.3 and
study intervals are divided into a series of
Developing stratigraphic frameworks is the
2.4 (Figure 2b). These units are defined
first order Chemostratigraphic Packages, 0-4,
key to the exploration and exploitation of any
by more subtle geochemical variations
based on changing values of CaO/Al2O3, Rb/
K2O, Fe2O3/MgO, Th/U and MgO/(CaO+MgO):
formation in any hydrocarbon basin. In shale
in CaO/Al2O3, Rb/K2O, Fe2O3/MgO, Th/U,
MgO/(CaO+MgO) and Zr/Nb ratios. The
plays, the more traditional methods used
Package 4 (approximately equivalent to
resultant Chemostratigraphic Package and
to define stratigraphic correlations in the oil

the Bossier Formation) is identified by
Chemostratigraphic Unit correlations are
industry are somewhat limited. Commonly, the
higher Th/U and MgO/(CaO+MgO) values
displayed on Figures 3 and 3b for wells
restricted basin nature of their accumulation

than underlying packages.
Watson-4, Glaspie Ocie GU-10, George T.W.
can limit the use of biostratigraphy, and

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| PESA News Resources | February/March 2012

shale exploration
another, the more closely linked they are in the
sediment. It is apparent from Figure 5 that the
elements fall into three broad groups:

Group 1 elements include CaO, MgO,

MnO and Sr, a grouping of elements
associated with carbonate minerals such
as calcite and dolomite.

Group 2 elements include Mo, U, Ni, V, Cu,

Zn and Co. These are all elements
associated with authigenic enrichment
under anoxic conditions (Tribovillard et
al., 2006).

Group 3 elements contain almost all other

elements and are associated with
terrigenous minerals, including clay
minerals (e.g. Al2O3, K2O, Th), quartz (SiO2),
feldspars (Na2O) and heavy minerals (e.g.
Zr, Hf ).

The significance of these element groupings

will be discussed further in Part 2 of this article.

Conclusions
Fig. 3. Correlation of wells Watson-4, Glaspie Ocie GU-10, George T.W. GUA8H, CGU 13-17 and Johnson Trust 1-2H based on the geochemical criteria
defined in Figure 2. Plot (A) shows the correlation of Chemostratigraphic
Packages and includes data from the formations over and underlying the
Haynesville Formation. Plot B focuses only on the Haynesville Formation and
shows the correlation of Chemostratigraphic Units within this formation.
Inset map shows relative positions of well in correlation panels.

GUA-8H, CGU 13-17 and Johnson Trust 1-2H.

High resolution stratigraphic

applications of whole rock
inorganic geochemical data in
shales
Although high resolution stratigraphic
frameworks are always desirable, the need
for them is exacerbated in shale plays by the
increased use of horizontal drilling in their
exploitation. Typically, the horizontal leg of a
well will be several thousand feet in length,
with the aim of remaining in a thin stratigraphic
horizon over as much of that distance as
possible. Figure 4 schematically shows how
the well-bore pathway through the Eagle Ford
Formation in a 'horizontal' sidetrack well can
be related back to the pilot hole by analysis of
cuttings samples. The ideal target zone for this
lateral well through the Eagle Ford Formation
is coincident with the geochemically defined
Unit 2.3 (Schmidt et al., 2010). At the top of
top Unit 2.3 (the top of the target zone) there
is a very marked downhole increase in P2O5
values, together with an increase in TiO2/Nb
and decrease in Th/U values. From the top of
this unit to its base, the P2O5 decreases and
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the TiO2/Nb increases, with the unit 2.3 / 2.2

boundary (base of target zone) being defined
by a decrease in TiO2/Nb values and an increase
in P2O5 values (Figure 4). By analysing cutting
samples from the horizontal offset to the
vertical hole the point at which the well bore
enters the target zone is clearly defined by the
sharp increase in P2O5 values around 15,800
(MD).

Geochemistry and mineralogy

The key to fully utilising major and trace
element changes in any ancient sequence is
understanding the geological controls on each
of the elements (Ratcliffe et al., 2007, Hildred
et al., 2011, Wright et al., 2010). A simple, but
effective way to achieve this is the consideration
of the Eigen-vector (EV) scores calculated
when PCA (principal component analysis) is
carried out on a geochemical dataset (Pearce
et al., 2005, Svendsen et al., 2007; Ellwood et
al., 2008; Pe-Piper et al., 2008, Ratcliffe et al.,
2010). One Figure 5, EV1 and EV2 scores, which
together account for 73% of the variation within
the entire Haynesville Formation dataset, are
plotted. On cross-plots such as that displayed on
Figure5, the more closely elements plot to one

In this first look at the application of elemental

data to helping develop shale resource
plays, the 'traditional' use of elemental data
for chemostratigraphy and its extension to
high resolution definitions for placement of
well-bores has been described. In the next
part of the article, the more unconventional
applications of mineral and TOC modelling,
identification of biogenic silica, recognition of
transgressive-regressive cycles and modelling
of paleoredox conditions will be discussed.

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Fig. 4. Using geochemical data to determine the well-bore pathway of a horizontal well relative to the
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Fig. 5. Eigen vector 1 (EV1) vs. Eigen vector 1 (EV2) calculated from data in the Haynesville Formation
from well George T.W GUA-8H. Elements fall into three broad groupings reflecting their mineralogical
associations in the formation.
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